CN102159755A - Method for producing nitride semiconductor crystal, nitride semiconductor crystal, and apparatus for producing nitride semiconductor crystal - Google Patents
Method for producing nitride semiconductor crystal, nitride semiconductor crystal, and apparatus for producing nitride semiconductor crystal Download PDFInfo
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- CN102159755A CN102159755A CN2010800026393A CN201080002639A CN102159755A CN 102159755 A CN102159755 A CN 102159755A CN 2010800026393 A CN2010800026393 A CN 2010800026393A CN 201080002639 A CN201080002639 A CN 201080002639A CN 102159755 A CN102159755 A CN 102159755A
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- C30B29/10—Inorganic compounds or compositions
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Abstract
Disclosed is a method for producing a nitride semiconductor crystal, wherein the following steps are performed. First of all, a crucible (101) within which a starting material (17) is placed is prepared. Then, a nitride semiconductor crystal is grown by depositing a starting material gas by heating and sublimating the starting material (17) within the crucible (101). In the preparation step, a crucible (101) which is formed from a metal that has a higher melting point than the starting material (17) is prepared.
Description
Technical field
The present invention relates to make the device of method, nitride semiconductor crystal and the manufacturing nitride semiconductor crystal of nitride semiconductor crystal.
Background technology
Aluminium nitride (AlN) crystal has wide energy bandgaps and the about 3.3WK of 6.2eV
-1Cm
-1High heat conductance and also have high resistance.Therefore, AlN crystal and other nitride semiconductor crystals have caused concern as the substrate material that is used for semiconducter device such as photoelectric device and microelectronic device.About the method for this nitride semiconductor crystal of growing, can use for example subliming method (for example, non-patent literature 1, patent documentation 1).
Non-patent literature 1 proposes to implement the following step.At first, AlN crystalline source material is placed in the crucible of being made by carbon.Secondly, carbonaceous crucible is heated to the temperature that makes the source material distillation.By making described source material distillation, the described thermogenesis sublimation gases body that adds makes it possible to the small AlN crystal of growth on powder or fine grain level.
Simultaneously, patent documentation 1 proposes, and utilizes following manufacturing installation (for example Fig. 4) to make nitride single-crystal.Promptly, described manufacturing installation has induction heating coil pipe as heating unit, is arranged in the reactor heating main body of described induction heating coil pipe inside and the crucible that is arranged in described reactor heating main body lower inside, and described crucible is used to hold the nitride single-crystal source material.Having put down in writing described crucible is made by graphite.
Reference listing
Patent documentation
Patent documentation 1: TOHKEMY 2006-27988 communique
Non-patent literature
Non-patent literature 1:Journal of Crystal Growth (crystal growth magazine) 34 volumes, 263-279 page or leaf (1976)
Technical problem
Yet, when the growing nitride semiconductor crystal,, use carbonaceous crucible about above-mentioned non-patent literature 1, about patent documentation 1, use plumbago crucible.When making that when crucible is heated nitride semiconductor crystal distils with source material, also can make the distillation of carbon and graphite.Under the sort of situation, the carbon of distillation or graphite are sneaked in the nitride-based semiconductor of growth.Consequential problem is that impurity is blended in the nitride semiconductor crystal of growth.
Therefore, the invention provides the nitride semiconductor crystal manufacture method that is used to make nitride semiconductor crystal, wherein suppress sneaking into of impurity, the invention enables the device that can obtain nitride semiconductor crystal and be used to make nitride semiconductor crystal simultaneously.
The means of dealing with problems
About nitride semiconductor crystal manufacture method of the present invention, implement the following step.At first, prepare to be used for carrying the crucible of source material in inside.In described crucible, heat described source material and make described source material distil, and by making the source material condensation of gas, the growing nitride semiconductor crystal.In described crucible preparation step, described crucible is made by the fusing point metal higher than the fusing point of described source material.
Nitride semiconductor crystal manufacturing installation of the present invention be make the distillation of the semi-conductive source material of nitrogenate and by the source material condensation of gas that makes distillation the device of growing nitride semiconductor crystal, and described device has crucible and heating unit.At described crucible internal layout source material.Described heating unit is disposed in the periphery of described crucible, and crucible inside is heated.Described crucible is made by the fusing point metal higher than the fusing point of described source material.
According to the manufacture method and the manufacturing installation of nitride semiconductor crystal, by fusing point than the high metal crucible of the fusing point of source material in the growing nitride semiconductor crystal.Thereby can suppress the distillation of crucible under the temperature of source material distillation.In addition, metal pair distillation gas is reactive low.In view of these reasons, can prevent that the material that constitutes crucible is blended in the nitride semiconductor crystal of growth.Therefore, can make sneaking into of impurity is controlled to be minimum nitride semiconductor crystal.
In above-mentioned nitride semiconductor crystal manufacture method, the step that forms coating member preferably is provided between crucible preparation step and growth step, described coating member covers the periphery of described crucible.
In above-mentioned nitride semiconductor crystal manufacturing installation, preferably between crucible and heating unit, arrange coating member.
Can prevent that thus impurity is blended into crucible inside from the coating member outside.Therefore, can make and further make the minimized nitride semiconductor crystal of sneaking into of impurity.
In above-mentioned nitride semiconductor crystal manufacture method, preferably, described coating member is made by the fusing point metal higher than the fusing point of described source material.
In above-mentioned nitride semiconductor crystal manufacturing installation, preferably, described coating member is made by the fusing point metal higher than the fusing point of described source material.
Thus, can suppress the distillation of coating member, thereby making to make makes the more minimized nitride semiconductor crystal of sneaking into of impurity.
Above-mentioned nitride semiconductor crystal manufacture method also be included in described coating member the peripheral disposition heater block step and at the peripheral disposition RF of heater block (radio frequency) coil pipe to heat the step of described heater block.
In above-mentioned nitride semiconductor crystal manufacturing installation, preferably, described heating unit is the RF coil pipe, and described device also has the heater block that is arranged between described coating member and the described heating unit.
The heat that is produced by the RF coil pipe is difficult for being absorbed by metal.Therefore, make heat be disposed in the heater block absorption of crucible periphery, make crucible to be heated because of the heat that heater block absorbs by the generation of RF coil pipe.Thus, source material can be distilled.Therefore, with above-mentioned same, can make sneaking into of impurity is controlled to be minimum nitride semiconductor crystal.
Above-mentioned nitride semiconductor crystal manufacture method preferably also is included in the step of the peripheral disposition lagging material of heater block, and described lagging material is made of the porosity material lower than the porosity of described heater block.
Above-mentioned nitride semiconductor crystal manufacturing installation preferably also has and is arranged in lagging material between described heater block and the described RF coil pipe, that be made of than the material of the porosity of heater block porosity.
Because the lagging material that constitutes by the porosity material lower in the peripheral disposition of heater block, so can prevent thermal runaway that heater block absorbs periphery to lagging material than the porosity of heater block.Can heat crucible effectively thus.Therefore, with above-mentioned same, can make sneaking into of impurity is controlled to be minimum nitride semiconductor crystal.
Make nitride semiconductor crystal of the present invention by any method in the above-mentioned nitride semiconductor crystal manufacture method.
According to nitride semiconductor crystal of the present invention, owing to when suppressing the crucible distillation, make crystal, so can obtain sneaking into of impurity to be controlled to be minimum nitride semiconductor crystal.
Above-mentioned nitride semiconductor crystal preferably has the diameter of 10mm at least and has the impurity concentration that is not more than 2ppm.
Make above-mentioned nitride semiconductor crystal by subliming method, this makes can realize having the above large diameter crystal of 10mm.And,, can realize the nitride semiconductor crystal of the low impurity concentration that 2ppm is following owing to when suppressing the crucible distillation, make described crystal.Therefore, can realize the nitride semiconductor crystal that surface-area is big and impurity concentration is low.
The invention effect
According to aforementioned,, utilize the fusing point metal crucible higher than the fusing point of source material according to nitride semiconductor crystal manufacture method of the present invention and manufacturing installation.Therefore, can prevent to be blended in the nitride semiconductor crystal of growth because of the impurity that the crucible distillation produces.Therefore, can make sneaking into of impurity is controlled to be minimum nitride semiconductor crystal.
Description of drawings
Fig. 1 is for representing the sectional view of nitride semiconductor crystal in the embodiment of the present invention in simplified form.
Fig. 2 is for representing the sectional view of nitride semiconductor crystal manufacturing installation in the embodiment of the present invention in simplified form.
Crucible and the peripheral sectional view thereof of Fig. 3 for representing that in simplified form the nitride semiconductor crystal manufacturing installation is comprised in the embodiment of the present invention.
Fig. 4 is presented at the schema of making the method for nitride semiconductor crystal in the embodiment of the present invention.
Fig. 5 is for being presented at the phantom view of the situation of growing nitride semiconductor crystal in the embodiment of the present invention in simplified form.
Fig. 6 is for showing the amplification sectional view of the nitride semiconductor crystal manufacturing installation of comparative example in simplified form.
Fig. 7 is for being presented at the sectional view of the different device that is used to make nitride semiconductor crystal in the embodiment of the present invention in simplified form.
Embodiment
Below, will describe embodiment of the present invention with reference to the accompanying drawings.Should be understood that in following explanation the identical or corresponding section in the accompanying drawing is with identical reference symbol mark, and no longer repeat to be described.
At first, with reference to figure 1, the nitride semiconductor crystal in one embodiment of the invention 10 is described.Described nitride semiconductor crystal 10 for example has diameter R and for example thickness H of at least 100 μ m of 10mm at least.The concentration of impurity is for for example being not more than 2ppm in described nitride semiconductor crystal 10.The impurity that constitutes described impurity concentration comprises for example C (carbon) and Si (silicon).The concentration of C is for for example being not more than 1ppm in described nitride semiconductor crystal 10, and the concentration of Si is for for example being not more than 1ppm simultaneously.
As long as nitride semiconductor crystal 10 is the semiconductor crystal of nitrogenous (N), then it is not subjected to particular restriction; Exemplarily, it is In
(1-x-y)Al
xGa
yN (0≤x≤1,0≤y≤1,0≤x+y≤1), and be preferably AlN, GaN (gan), InN (indium nitride) etc.; More preferably described crystal is AlN.
Next, with reference to figure 2 and 3, the device 100 that is used to make nitride semiconductor crystal 10 in one embodiment of the invention is described.Described manufacturing installation 100 is for by making the distillation of the semi-conductive source material of nitrogenate make the source material condensation of gas that distils become crystal, thus the device of growing nitride semiconductor crystal 10.
As shown in Fig. 2 and 3, the manufacturing installation 100 in the present embodiment mainly comprises crucible 101, the overlapping casing tube 110 as coating member, heater block 121, lagging material 127, reaction vessel 123 and heating unit 125.
Described crucible 101 is the position of placing source material 17 and base substrate 11 in inside.Described crucible 101 is preferably made by the fusing point metal higher than the fusing point of described source material 17.For example, this metal can be tantalum (Ta), tungsten (W) or rhenium (Re) and alloy thereof.In other words, described crucible 101 does not contain the C atom.Thereby can reduce the distillation of material under the temperature of source material distillation that constitutes crucible 101.In addition, the described distillation gas of metal pair is reactive low.And this metal is favourable, but because its radiant ratio height, because its thermotolerance height and because its be the material of industrial utilization.Especially, preferred crucible 101 be Ta, because its reactive low to nitride-based semiconductor, and it at high temperature has the thermotolerance of excellence.Herein, above-mentioned " fusing point " is meant the fusing point under 1 normal atmosphere.
Crucible 101 also has venting port 101a.Described venting port 101a is disposed to the impurity of crucible 101 inside the outside of crucible 101.Can suppress misgrowth for crucible provides venting port 101a, thereby make growing single-crystal nitride semiconductor crystal easily.
Around crucible 101, arrange overlapping casing tube 110, thereby coat crucible 101.In the present embodiment, inlet mouth 123c and venting port 123d by reaction vessel 123, described overlapping casing tube 110 keeps reaction vessel 123 and outside ventilation, and described overlapping casing tube 110 is enclosed in crucible 101 in inlet mouth 123c and the venting port 123d zone in addition.Especially, arrange described overlapping casing tube 110 and keep at a certain distance away that simultaneously except inlet mouth 123c and venting port 123d place, described crucible 101 is capped sleeve pipe 110 and reaction vessel 123 seals with crucible 101.By this way, overlapping casing tube 110 prevents that the heater block 121 of impurity from overlapping casing tube 110 outsides, lagging material 127, reaction vessel 123 etc. from invading in the crucible 101.
It should be noted that the structure that overlapping casing tube 110 should be restricted to above-mentioned airtight described crucible 101.That is, even overlapping casing tube 110 does not seal crucible 101, it also will have above-mentioned effect.For example, as shown in Figure 7, in manufacturing installation 100, described overlapping casing tube 110 can have opening in top and bottom.Similarly, in the manufacturing installation (not shown), described coating member 110 can be in the upper end or the lower end have opening.In this case, by making gas flow into the inside of overlapping casing tube 110, will the performance effect identical with above-mentioned closed structure, thus can prevent in the intrusion crucibles 101 such as the heater block 121 of impurity from overlapping casing tube 110 outsides, lagging material 127, reaction vessel 123.
Described overlapping casing tube 110 is preferably made by the fusing point metal higher than the fusing point of described source material.For example, this metal can be Ta, W or Re and alloy thereof, and is identical with the material that constitutes crucible 101, and preferred described parts are made by Ta simultaneously.Ta is difficult for the fact with the C reaction, even make and contain in the situation of C at heater block 121 and lagging material 127, overlapping casing tube 110 and the reaction of the C that has distilled and sneaked into from heater block 121 and lagging material 127 is minimized.Even and contain in the situation of Si at reaction vessel 123, overlapping casing tube 110 also can make the reaction with the Si that has distilled and sneaked into from reaction vessel minimize.Described overlapping casing tube 110 can be and crucible 101 identical materials, or it can be different material.Should be understood that described overlapping casing tube 110 can omit.
At the peripheral disposition heater block 121 of described overlapping casing tube 110, and in the present embodiment, arrange described heater block 121 in the mode that contacts with overlapping casing tube 110.From heating unit 125, absorb heat and crucible 101 inside are heated as the heater block 121 of DB.From the viewpoint of excellent heat resistance, described heater block 121 exemplarily contains C, and for example it is made of graphite.Should be understood that described heater block 121 can omit.
At the peripheral disposition lagging material 127 of described heater block 121, and in the present embodiment, make the mode that covers described heater block 121 whole peripheries arrange described lagging material 127 to contact with heater block 121.Described lagging material 127 is made than the material of the porosity low (having lower porosity) of heater block 121 by porosity.Described lagging material 127 prevents that the thermal runaway of heater block 121 absorptions is to outside.Should be understood that lagging material 127 self is difficult for from heating unit 125 heat absorptions.From the viewpoint of excellent heat resistance, described lagging material 127 exemplarily contains C, and for example described lagging material 127 is made of the carbon felt that is rolled into the concentric(al) circles form.Should be understood that described lagging material 127 can omit.
In described lagging material 127 arranged around are reaction vessels 123.Described manufacturing installation 100 has inlet mouth 123a and 123c, and described inlet mouth 123a and 123c (are the lower end) in an end of reaction vessel 123 and form and be used to make carrier gas such as gaseous nitrogen (N in the present embodiment
2) flow into for example reaction vessel 123 inside, and described manufacturing installation 100 has venting port 123b and 123d, and described venting port 123b and 123d form in another end of described reaction vessel 123 (being the upper end in the present embodiment) and be used for carrier gas is disposed to reaction vessel 123 outsides.Described inlet mouth 123a and venting port 123b are arranged in the outside of the overlapping casing tube 110 in the described reaction vessel 123.Described inlet mouth 123c and venting port 123d are arranged in the inside of the overlapping casing tube 110 in the described reaction vessel 123.This means that inlet mouth 123c makes carrier gas flow into and is arranged in the crucible 101 of reaction vessel 123 inside.And venting port 123d is disposed to carrier gas, impurity etc. the outside of reaction vessel 123 from crucible 101.Should be understood that described reaction vessel 123 can omit.
At the described heating unit 125 of the peripheral disposition of described crucible 101, there the inside of described crucible 101 is heated.Because the crucible 101 in the present embodiment is positioned at the middle part of reaction vessel 123 inside, so heating unit 125 is arranged in along in the middle part in reaction vessel 123 outsides.About heating unit 125, can use for example RF coil pipe, resistive heating coil pipe etc.In the situation of utilizing the RF coil pipe, thus the inside of heater block 121 being heated heating crucible 101.In the situation of utilizing the resistive heating coil pipe, the inside of direct heating crucible 101.In view of described reason,, can omit heater block 121 and lagging material 127 in that the resistive heating coil pipe is used as in the situation of heating unit 125.
In addition,, provide pyrometer 129a and 129b, with the temperature (along the temperature of source material 17) of measurement crucible 101 upper ends and the temperature (along the temperature of base substrate 11) of its lower end in the upper and lower of reaction vessel 123.Should be understood that pyrometer 129a and 129b can omit.
Although should be understood that except above-mentioned parts, above-mentioned manufacturing installation 100 also can comprise multiple parts, for convenience of explanation, has omitted the diagram and the explanation of this parts.
Next, the method for making nitride semiconductor crystal 10 in the embodiment of the present invention is described.In the present embodiment, make nitride semiconductor crystal 10 by the subliming method of utilizing the manufacturing installation 100 shown in Fig. 2 and 3.
At first, prepare the crucible 101 at positioned inside source material 17 of being used for as shown in Fig. 2 and 3, described crucible 101 is made by the fusing point metal higher than the fusing point of source material 17.Secondly, form overlapping casing tube 110 with as coating member in crucible 101 peripheries.Preferably, described overlapping casing tube 110 is made by the fusing point metal higher than the fusing point of described source material 17.Then, at the peripheral disposition heater block 121 of overlapping casing tube 110.Next, at the peripheral disposition lagging material 127 of heater block 121, described lagging material 127 is made of the porosity material lower than the porosity of heater block 121.Then, at the peripheral disposition reaction vessel 123 of lagging material 127.Heating unit 125 put into the position that surround reaction vessel 123 thereafter.In a word, with reference to figure 4, the manufacturing installation 100 (step S1) in the present embodiment shown in the set-up dirgram 2 and 3.
Next, as shown in Fig. 2～4, configuration base substrate 11 (step S2).Although described base substrate is not carried out particular restriction, be preferably the atomic ratio substrate identical with the atomic ratio of the nitride semiconductor crystal of growth.Described base substrate 11 is placed on the top of crucible 101.Should be understood that step S2 can omit.Under the sort of situation, can be by the sporadic nucleation described nitride semiconductor crystal of growing.
Then, source of configuration material 17 (step S3).Although described source material 17 is not carried out particular restriction, preferred its purity level height.For example, be in the A1N crystalline situation at the nitride semiconductor crystal of growing, preferably agglomerating AlN source material is used as source material 17.Under the sort of situation, in described source material 17, do not comprise sintering aid.Described source material 17 is placed on the bottom of crucible 101, itself and base substrate 11 are faced mutually.
Then, as shown in Figures 4 and 5, described source material 17 is heated, thereby make described material distillation, and in the zone of crucible 101 inside relative, described condensation of material is become crystal, thereby growing nitride semiconductor crystal 10 (step 4) with described source material 17.In the present embodiment, by the sublimation source material gas and make it be condensate in growing nitride semiconductor crystal 10 on the base substrate.
In this step S4, in the situation of growth A1N crystal, heating unit 125 is controlled, for example as nitride semiconductor crystal 10, make that along the temperature of base substrate 11 be 1400 ℃～1800 ℃, and make that along the temperature of described source material 17 be 1850 ℃～2150 ℃.In the situation of growing GaN crystal as nitride semiconductor crystal 10, heating unit 125 is controlled, for example, make that along the temperature of base substrate 11 be 1450 ℃～1550 ℃, and make that along the temperature of described source material 17 be 1600 ℃～1700 ℃.
About this step S4, the preferred overlapping casing tube 110 that the is arranged in crucible 101 peripheries nitride semiconductor crystal 10 of growing that utilizes.In subliming method,, be easy to distillation so constitute the material that is positioned at overlapping casing tube 10 external heated parts 121, lagging material 127 and reaction vessel 123 owing to growing nitride semiconductor crystal 10 under aforesaid high temperature.Yet, arrange that described overlapping casing tube 110 can prevent that the impurity that distils is blended into crucible 101 inside.
In the situation of the overlapping casing tube 110 growing nitride semiconductor crystals of outside utilization is arranged in crucible 101, placing 10, along the carrier gas of interior all side flow of overlapping casing tube 110 (from inlet mouth 123c flow into and by venting port 123d expellant gas) and can be identical or different along the peripheral side mobile carrier gas (from inlet mouth 123a inflow and by venting port 123b expellant gas) of described overlapping casing tube 110.Preferably, gaseous nitrogen is along interior all side flow of the overlapping casing tube 110 in the reaction vessel 123, and the gas except gaseous nitrogen is mobile along the peripheral side of the overlapping casing tube 110 in the described reaction vessel 123.As peripheral side mobile gas along overlapping casing tube 110, preferred flow rare gas element such as gaseous state argon (Ar).Under the sort of situation, can suppress the generation of prussic acid (HCN) gas, therefore do not need the Hazardous wastes removal device.
It should be noted that in the situation of using base substrate 11 growing nitride semiconductor crystals 10 the preferred step of implementing to remove base substrate 11.
By abovementioned steps S1～S4, the nitride semiconductor crystal 10 shown in can shop drawings 1.In the present embodiment, under the situation of the distillation of the material that suppress to constitute crucible 101, make nitride semiconductor crystal 10.Therefore can suppress in the nitride semiconductor crystal 10 that impurity is blended into manufacturing.Especially, the overlapping casing tube 110 that is arranged in crucible 101 peripheries by the utilization nitride semiconductor crystal 10 of growing, can prevent that impurity is blended in the nitride semiconductor crystal 10 of manufacturing, described impurity source is from the distillation of the material that constitutes the parts that are positioned at crucible 101 peripheries.And, make the fact of nitride semiconductor crystal 10 by subliming method, make the nitride semiconductor crystal 10 that can make high surface area.Therefore, can Production Example as having at least the 10mm diameter and having the nitride semiconductor crystal 10 that is not more than the 2ppm impurity concentration.
Therefore, can be used as the device substrate ideally with passing through the nitride semiconductor crystal manufacture method of the present embodiment and the nitride semiconductor crystal 10 of the low impurity concentration that manufacturing installation 100 is made, described device for example comprises: optics such as photodiode and laser diode; Semi-conductor electronic device such as rectifier, bipolar transistor, field-effect transistor and High Electron Mobility Transistor (HEMT); Field emission device; Semiconductor transducer such as temperature sensor, pressure transmitter, radiation sensor and visible-UV-detector; And surface acoustic wave device (SAW device), vibrator, syntonizer, vibrator, MEMS (micro electro mechanical system) (MEMS) parts and piezo-activator.Especially, because nitride semiconductor crystal 10 that can manufacturing defect is few, dislocation desity is low and light-transfer characteristic is excellent, so it can be advantageously used in the luminous semiconductor device.
Embodiment 1
In the present embodiment, study utilizing by the effect of the fusing point metal crucible manufacturing nitride semiconductor crystal higher than the fusing point of source material.
Example 1 of the present invention
According to above-mentioned embodiment, utilize the manufacturing installation 100 shown in Fig. 1 and 2 to make the nitride semiconductor crystal 10 of example 1 of the present invention.
Particularly, at first, prepare manufacturing installation 100, described manufacturing installation 100 has the crucible of being made by Ta 101 (step S1).Herein, described heater block 121 is made of graphite, and described lagging material 127 is made of the carbon felt simultaneously.In addition, about reaction vessel 123, use silica tube.And overlapping casing tube 110 is made of Ta.
Then, will be configured in the inside (step S3) of crucible 101 as the A1N of source material 17.The fusing point that constitutes the material Ta of crucible 101 is 2990 ℃, and the fusing point of source material AlN is 2200 ℃ simultaneously, and the fusing point of wherein said crucible 101 is than the fusing point height of source material 17.
Then, at the AlN substrate of crucible 101 internal layout, make itself and source material 17 relative (step S2) as base substrate 11.
Then, flow through gaseous state N as carrier gas
2, at N
2Under the atmosphere, under 2000 ℃ growth temperature, growth is as the AlN crystal (step S4) of nitride semiconductor crystal 10.
After cooling, the AlN crystal of example 1 of the present invention is taken out from manufacturing installation 100.The result is the AlN crystal that has formed the example of the present invention 1 with 1mm thickness on base substrate 11.
Comparative example 1
Made the nitride semiconductor crystal of comparative example 1 in identical with example of the present invention 1 basically mode, but difference is that the material that constitutes crucible 101 is carbon and overlapping casing tube 110 is not installed.
Particularly, use the manufacturing installation shown in Fig. 6 to make the AlN crystal of comparative example 1.That is, the manufacturing installation that is used for comparative example 1 has carbonaceous crucible 201, covers the heater block 121 of crucible 201 peripheries and the lagging material 127 that covers heater block 121 peripheries.Thus, on base substrate 11, made the AlN crystal of comparative example 1 with 1mm thickness.
Comparative example 2
Made the nitride semiconductor crystal of comparative example 2 in identical with example of the present invention 1 basically mode, but difference is that the material that constitutes crucible 101 is TaC (tantalum carbide) and overlapping casing tube 110 is not installed.
Particularly, in the manufacturing installation shown in Fig. 6, be used for the crucible that is made of TaC of comparative example 1, the material of wherein said crucible 101 is Ta: C=1: 1.Thus, on base substrate 11, made the A1N crystal of comparative example 2 with 1mm thickness.
Measuring method
Use SIMS to measure in the AlN crystal of example 1 of the present invention and comparative example 1 and 2 Si concentration, C concentration and O concentration as impurity concentration.Show the result in down in the Table I.
Table I
| C concentration | Si concentration | O concentration | Impurity concentration | |
| Example 1 of the present invention | Below the 1ppm | Below the 1ppm | 0ppm | Below the 2ppm |
| Comparative example 1 | 10ppm | 10ppm | 0ppm | 20ppm |
| Comparative example 2 | 5ppm | 5ppm | 0ppm | 10ppm |
Measuring result
As shown in Table I, in the AlN of example 1 of the present invention crystal, the concentration of C and the concentration of Si are not more than 1ppm separately, the concentration of impurity is very low simultaneously, be not more than 2ppm, wherein utilize by not containing C and the fusing point metal crucible 101 higher and make the AlN crystal of example 1 of the present invention than the fusing point of source material 17.
On the other hand, in the AlN crystal of the comparative example 1 that uses the crucible manufacturing of being made by carbon, the concentration of C and the concentration of Si are 10ppm, and impurity concentration is very high, is 20ppm.
In the AlN crystal of the comparative example 2 that uses the crucible manufacturing of being made by TaC, although the concentration of the concentration of C, Si and impurity concentration are lower than the described concentration of AlN crystalline of comparative example 1, they all are higher than the AlN crystalline impurity concentration of example 1 of the present invention.
As long as relate to carbon, then constitute the material distillation of crucible 201, heater block 121 and lagging material 127 and be blended in the AlN crystal by the venting port 101a in the crucible 101.As long as relate to silicon, then constitute the material distillation of reaction vessel 123 and be blended in the AlN crystal by the venting port 101a in the crucible 101.Therefore,, should be understood that and utilize the material that constitutes crucible 101, can reduce the concentration of C according to the result of carbon concentration.According to the result of silicon concentration, should be understood that by overlapping casing tube 110 is installed, can reduce the concentration of Si.
Wherein, the inventor obtains following opinion: do not provide venting port 101a for crucible 101 if crucible 101 inside are airtight fully, then crystal growth can generate monocrystalline unusually and not.Therefore, must in crucible 101, form venting port 101a.Therefore, should be understood that by making the material that constitutes crucible 101 different with comparative example, can be in can not excrescent AlN crystal the concentration of reduction impurity.
Confirm according to above-mentioned,, utilize the AlN crystal of making as nitride semiconductor crystal 10 by the fusing point metal crucible 101 higher, make and to reduce the impurity concentration that comprises in the AlN crystal of manufacturing than the fusing point of source material according to present embodiment.
In the present embodiment, to as the example of nitride semiconductor crystal 10 and the AlN crystal that provides describe.Yet,,, can prevent that crucible 101 from distilling under the temperature of source material 17 distillations by the material that constitutes crucible 101 is provided in the same manner about the nitride semiconductor crystal except the AlN crystal 10.In addition, metal pair distillation gas is reactive low.Therefore, in addition about the nitride semiconductor crystal except the A1N crystal 10, the material that can suppress to constitute crucible 101 equally is blended in the nitride semiconductor crystal of growth.Therefore, in the mode identical, can make and make the minimized nitride semiconductor crystal 10 of sneaking into of impurity with embodiment 1.
Embodiment 2
In the present embodiment, in having the manufacturing installation of coating member, the gas of nonnitrogenous gas is studied along the peripheral side mobile effect of coating member.
Sample 1～3
About sample 1～3, utilize the manufacturing installation 100 of example 1 of the present invention to make the AlN crystal basically, but difference is, make gaseous state N as carrier gas
2Along interior all side flow of the overlapping casing tube 110 in the reaction vessel 123, and gaseous helium (He), gaseous state neon (Ne) and gaseous state Ar are flowed along the peripheral side of the overlapping casing tube 110 in the reaction vessel 123.
Flow through therein in the various AlN crystalline manufacturings of various carrier gas, utilize the prussic acid gas sensor to measure the prussic acid gas concentration of reaction vessel 123 inside.And, therein along the peripheral side and the mobile gaseous state N of interior all sides of overlapping casing tube 110
2The AlN crystalline of example of the present invention 1 make, measured the prussic acid gas concentration of reaction vessel 123 inside in an identical manner.Show the result in the Table II.
Table II
As shown in Table II, along in the peripheral side mobile sample of coating member, the concentration of the prussic acid gas that produces in the AlN crystalline is made proof is less than 1ppm at the rare gas element except that gaseous nitrogen; Almost do not produce prussic acid gas.On the other hand, along in the peripheral side mobile sample of coating member, detected the prussic acid gas of 30ppm at nitrogen.Therefore, should be understood that the rare gas element that makes except that gaseous nitrogen is mobile along the peripheral side of coating member, can omit the Hazardous wastes removal device that is used to remove all prussic acid gas danger.
Confirm according to above-mentioned,, in having the manufacturing installation of coating member, make the gas except that gaseous nitrogen can simplify manufacturing installation along the peripheral side of coating member is mobile according to present embodiment.
Although in the above described manner embodiment of the present invention and embodiment are illustrated, from beginning to expect the feature appropriate combination of various embodiments and embodiment.In addition, disclosed embodiment and embodiment should be considered to exemplary and nonrestrictive in every respect now.Scope of the present invention is not to be limited by above-mentioned embodiment and embodiment but limited by the scope of claims, and is intended to comprise implication and all modifications in described scope that is equal to claims scope.
Reference numeral:
10: nitride semiconductor crystal
11: base substrate
17: source material
100: manufacturing installation
101: crucible
101a: exhaust outlet
110: overlapping casing tube
121: heater block
123: reaction vessel
123a, 123c: inlet mouth
123b, 123d: venting port
125: heating unit
127: lagging material
129a, 129b: pyrometer
H: thickness
R: diameter
Claims (12)
1. method of making nitride semiconductor crystal (10), described method comprises:
Preparation is used for the step at the crucible (101) of inside carrying source material; With
In described crucible, make described source material (17) distillation, and make the source material condensation of gas, thus the step of growing nitride semiconductor crystal by heating described source material; Wherein
In described preparation step, prepare by the fusing point metal crucible (101) higher than the fusing point of described source material (17).
2. the method for manufacturing nitride semiconductor crystal as claimed in claim 1 (10), described method also comprises between the step of described preparation crucible and described growth step: form the step that covers the peripheral coating member (110) of described crucible (101).
3. the method for manufacturing nitride semiconductor crystal as claimed in claim 2 (10), wherein said coating member (110) is made than the high metal of fusing point of described source material (17) by fusing point.
4. the method for manufacturing nitride semiconductor crystal as claimed in claim 2 (10) also comprises:
Step at the peripheral disposition heater block (121) of described coating member (110); With
At the peripheral disposition RF coil pipe of described heater block (121) to heat the step of described heater block (121).
5. the method for manufacturing nitride semiconductor crystal as claimed in claim 4 (10), also comprise: in the step of the peripheral disposition lagging material (127) of described heater block (121), described lagging material (127) is made of the porosity material lower than the porosity of described heater block (121).
6. a nitride semiconductor crystal (10), it is by the method manufacturing of the described manufacturing nitride semiconductor crystal of claim 1 (10).
7. nitride semiconductor crystal as claimed in claim 6 (10), it has the diameter of 10mm at least, and has the impurity concentration that is not more than 2ppm.
8. device (100) of making nitride semiconductor crystal (10), make the semi-conductive source material of nitrogenate (17) distillation by described device (100), and by the source material condensation of gas that makes distillation growing nitride semiconductor crystal (10), described device comprises:
Be used for crucible (101) at inside carrying source material (17); With
Be arranged in described crucible (101) periphery and be used to heat the inner heating unit (125) of described crucible (101); Wherein
Described crucible (101) is made than the high metal of fusing point of described source material (17) by fusing point.
9. the device (100) of manufacturing nitride semiconductor crystal as claimed in claim 8 (10) also comprises the coating member (110) that is arranged between described crucible (101) and the described heating unit (125).
10. the device (100) of manufacturing nitride semiconductor crystal as claimed in claim 9 (10), wherein said coating member (110) is made than the high metal of fusing point of described source material (17) by fusing point.
11. the device (100) of manufacturing nitride semiconductor crystal as claimed in claim 9 (10), described heating unit (125) is the RF coil pipe,
Also comprise the heater block (121) that is arranged between described coating member (110) and the described heating unit (125) in the described device (100).
12. the device (100) of manufacturing nitride semiconductor crystal as claimed in claim 11 (10) also comprises and is arranged in lagging material (127) between described heater block (121) and the described RF coil pipe, that be made of the porosity material lower than the porosity of described heater block.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009007394 | 2009-01-16 | ||
| JP2009-007394 | 2009-01-16 | ||
| JP2009-293994 | 2009-12-25 | ||
| JP2009293994A JP5418210B2 (en) | 2009-01-16 | 2009-12-25 | Nitride semiconductor crystal manufacturing method, AlN crystal and nitride semiconductor crystal manufacturing apparatus |
| PCT/JP2010/050257 WO2010082574A1 (en) | 2009-01-16 | 2010-01-13 | Method for producing nitride semiconductor crystal, nitride semiconductor crystal, and apparatus for producing nitride semiconductor crystal |
Publications (2)
| Publication Number | Publication Date |
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| CN102159755A true CN102159755A (en) | 2011-08-17 |
| CN102159755B CN102159755B (en) | 2014-06-11 |
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| CN201080002639.3A Expired - Fee Related CN102159755B (en) | 2009-01-16 | 2010-01-13 | Method for producing nitride semiconductor crystal, nitride semiconductor crystal, and apparatus for producing nitride semiconductor crystal |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20110265709A1 (en) |
| EP (1) | EP2390386B1 (en) |
| JP (1) | JP5418210B2 (en) |
| KR (1) | KR20110116114A (en) |
| CN (1) | CN102159755B (en) |
| WO (1) | WO2010082574A1 (en) |
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| JP5418236B2 (en) | 2009-01-23 | 2014-02-19 | 住友電気工業株式会社 | Nitride semiconductor crystal manufacturing apparatus, nitride semiconductor crystal manufacturing method, and aluminum nitride crystal |
| JP2011256063A (en) * | 2010-06-07 | 2011-12-22 | Bridgestone Corp | Single crystal production apparatus |
| US20140264388A1 (en) * | 2013-03-15 | 2014-09-18 | Nitride Solutions Inc. | Low carbon group-iii nitride crystals |
| DE102016106734A1 (en) * | 2015-12-14 | 2017-06-14 | Osram Opto Semiconductors Gmbh | Support for an optoelectronic component, method for producing a support for an optoelectronic component, wafers and soldering methods |
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| US20030127044A1 (en) * | 2001-09-21 | 2003-07-10 | Schowalter Leo J. | Powder metallurgy tungsten crucible for aluminum nitride crystal growth |
| CN1717508A (en) * | 2003-07-31 | 2006-01-04 | Si晶体股份公司 | Method and device for AIN single crystal production with gas-permeable crucible walls |
| US20060005763A1 (en) * | 2001-12-24 | 2006-01-12 | Crystal Is, Inc. | Method and apparatus for producing large, single-crystals of aluminum nitride |
| US20070256630A1 (en) * | 2006-05-04 | 2007-11-08 | Fairfield Crystal Technology, Llc | Method and apparatus for aluminum nitride monocrystal boule growth |
| CN101297397A (en) * | 2003-07-11 | 2008-10-29 | 克利公司 | Semi-insulating GaN and method of making the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6770135B2 (en) * | 2001-12-24 | 2004-08-03 | Crystal Is, Inc. | Method and apparatus for producing large, single-crystals of aluminum nitride |
| JP4736365B2 (en) | 2004-07-21 | 2011-07-27 | 学校法人早稲田大学 | Method for producing aluminum nitride single crystal |
| JP2007145679A (en) * | 2005-11-30 | 2007-06-14 | Fujikura Ltd | Apparatus for and method of producing aluminum nitride single crystal |
| JP5045232B2 (en) * | 2006-06-20 | 2012-10-10 | 住友電気工業株式会社 | AlxGa1-xN crystal growth method |
-
2009
- 2009-12-25 JP JP2009293994A patent/JP5418210B2/en active Active
-
2010
- 2010-01-13 US US13/063,937 patent/US20110265709A1/en not_active Abandoned
- 2010-01-13 KR KR1020117002960A patent/KR20110116114A/en not_active Application Discontinuation
- 2010-01-13 EP EP10731243.1A patent/EP2390386B1/en not_active Not-in-force
- 2010-01-13 WO PCT/JP2010/050257 patent/WO2010082574A1/en active Application Filing
- 2010-01-13 CN CN201080002639.3A patent/CN102159755B/en not_active Expired - Fee Related
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| US20030127044A1 (en) * | 2001-09-21 | 2003-07-10 | Schowalter Leo J. | Powder metallurgy tungsten crucible for aluminum nitride crystal growth |
| US20060005763A1 (en) * | 2001-12-24 | 2006-01-12 | Crystal Is, Inc. | Method and apparatus for producing large, single-crystals of aluminum nitride |
| CN101297397A (en) * | 2003-07-11 | 2008-10-29 | 克利公司 | Semi-insulating GaN and method of making the same |
| CN1717508A (en) * | 2003-07-31 | 2006-01-04 | Si晶体股份公司 | Method and device for AIN single crystal production with gas-permeable crucible walls |
| US20070256630A1 (en) * | 2006-05-04 | 2007-11-08 | Fairfield Crystal Technology, Llc | Method and apparatus for aluminum nitride monocrystal boule growth |
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| D. CAI ET.AL.: "Effect of thermal environment evolution on AlN bulk sublimation crystal growth", 《JOURNAL OF CRYSTAL GROWTH》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102159755B (en) | 2014-06-11 |
| WO2010082574A1 (en) | 2010-07-22 |
| EP2390386A1 (en) | 2011-11-30 |
| EP2390386B1 (en) | 2015-08-12 |
| KR20110116114A (en) | 2011-10-25 |
| JP2010184857A (en) | 2010-08-26 |
| US20110265709A1 (en) | 2011-11-03 |
| JP5418210B2 (en) | 2014-02-19 |
| EP2390386A4 (en) | 2013-08-28 |
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